Prepared by: ASL Analytical Service Laboratories Ltd., Vancouver, British Columbia. Prepared for:

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1 Ministry of Environment, Lands and Parks BRITISH COLUMBIA MINISTRY OF THE ENVIRONMENT, LANDS, AND PARKS PETROLEUM HYDRDROCARBON METHODS STUDY (1998) ROUND ROBIN AND SINGLE LABORATORY RESULTS FINAL REPORT Prepared by: ASL Analytical Service Laboratories Ltd., Vancouver, British Columbia Prepared for: Pollution Prevention & Remediation Branch, Ministry of Environment, Lands, and Parks Province of British Columbia June 30, 1999 Her Majesty the Queen in Right of the Province of British Columbia 1999 All Rights Reserved

2 EXECUTIVE SUMMARY In July of 1998, private and government laboratories in British Columbia and Alberta were requested by the British Columbia Ministry of the Environment, Lands, and Parks (BCMELP) to participate in a Petroleum Hydrocarbon round robin quality assurance study. The purpose of the study was to evaluate the performance and associated variability of BC Environment s new analytical methods for Petroleum Hydrocarbons (Draft 2.0, October 1998). Nine laboratories participated in the round robin study, which evaluated the new hydrocarbon methods using eight Reference Samples containing petroleum hydrocarbons, and seven Quality Control (QC) samples that are daily QC requirements specified by the methods. Where applicable, Polycyclic and Monocyclic Aromatic Hydrocarbons (PAH and MAH) were evaluated in addition to the aggregate hydrocarbon parameters described in the methods. Replicate analyses (n 6) were performed by ASL Analytical Service Laboratories for the same fifteen samples, and are included in this report as Single Laboratory Data. Overall reproducibility of results obtained for both the round robin and the single laboratory components were very good. Comparative equivalency was excellent between the means of the round robin and single laboratory data. For the eight Reference Samples, the round robin precision for the hydrocarbon parameters was surprisingly good, returning relative standard deviations ranging from %. This degree of variability was significantly better than the round robin precision seen for the PAH and MAH target compounds (an unexpected finding). As expected, single laboratory data was considerably more precise than round robin data. For the petroleum product Reference Samples, methodological accuracy could not be directly evaluated, since the true values for the hydrocarbon parameters are not known. Results for the Reference Samples are summarized in Table 1. The results obtained for the seven method QC samples indicate that the QC acceptance criteria specified in the methods are reasonable and can be met by the majority of laboratories without undue effort or difficulty. The BCMELP Hydrocarbon Methods The Draft 2.0 hydrocarbon methods incorporate stakeholder input received following public release for comment of the Draft 1.0 methods in July, Four analytical test methods were evaluated within this study: Volatile Hydrocarbons (VH) in Solids Volatile Hydrocarbons (VH) in Water Extractable Petroleum Hydrocarbons (EPH) in Solids Extractable Petroleum Hydrocarbons (EPH) in Water Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 2 of 48

3 The new BC Hydrocarbon Methods were designed as Performance Based Methods. However, because the VH and EPH parameters are method-defined, critical elements within each method have been prescribed and are mandatory. This is necessary to ensure reasonable inter-laboratory comparability. Laboratories will be permitted to modify non-critical elements of the methods if they are able to verify and document that the modified procedure can provide results equivalent to that of the reference method. Requirements for demonstrating equivalence of alternate procedures are described within each method. Round Robin Objectives The primary objective of the round robin study was to evaluate the inter-laboratory variability of the draft hydrocarbon methods. The study was not intended to assess the proficiency of participating laboratories, nor was it intended to demonstrate the equivalence of any alternate or modified procedures. Therefore, all participating laboratories were asked to follow the methods as written, as closely as possible, with no significant modifications. In several instances, participating laboratories submitted results generated from modified procedures. Data generated by procedures that did not follow one or more prescribed elements of a particular method were excluded from statistical evaluation. However, these data are reported in Appendix A. In addition to the four analytical test methods, two new calculation procedures were also evaluated: Calculation of Volatile Petroleum Hydrocarbons (VPH) in Solids or Water Calculation of Light and Heavy Extractable Petroleum Hydrocarbons (LEPH & HEPH) in Solids or Water The parameters VPH, LEPH, and HEPH are scheduled substances under the Contaminated Sites Regulation. They are calculated parameters, determined by subtracting specified target parameter results from VH or EPH results. To allow evaluation of the VPH and LEPH/HEPH calculation procedures, the round robin study included the analysis of Mononuclear Aromatic Hydrocarbons (MAH) for all VH samples, and included the analysis of Polynuclear Aromatic Hydrocarbons (PAH) for all EPH samples. The methods used to determine MAH and PAH are not directly evaluated in this study. However, their analysis is nevertheless an integral component of the new methodologies. Therefore, participating laboratories were asked to provide information about the methods used to determine these parameters. Round Robin Organization and Administration Environment Canada s Pacific Environmental Science Center (PESC) was contracted by BCMELP to coordinate and administer the round robin. ASL Analytical Service Laboratories (ASL), the author of the new hydrocarbon methods, was contracted to design the study, to source and prepare all round robin sample materials, to prepare instructions to participants, and to complete this report. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 3 of 48

4 In late November 1998, round robin study materials were distributed by PESC to laboratories that had agreed to participate in the study. Of the twenty-two SCC/CAEAL accredited and certified laboratories in BC and Alberta 1, ten laboratories requested and received round robin materials. A total of nine laboratories ultimately contributed results to the round robin. The names of these participating laboratories are listed below. PARTICIPATING LABORATORIES: AGAT Laboratories AGRA Earth & Environmental Limited ASL Analytical Service Laboratories Ltd. Can Test Ltd. Enviro-Test Laboratories Levelton Analytical Service Maxxam Analytic Inc. Norwest Labs Philip Analytical Services Corporation Calgary, AB Edmonton, AB Vancouver, BC Vancouver, BC Edmonton, AB Richmond, BC Calgary, AB Surrey, BC Burnaby, BC Each participant was provided with a distribution package that included the following: A copy of the BCMELP Petroleum Hydrocarbon methods (Draft 2.0, October 98). Round robin study samples and spike solutions. Detailed instructions to participants. By mid January 1999, PESC had received results from participating laboratories in both electronic and hard copy format. Several laboratories used procedures that contravened prescribed (i.e. required) elements of one or more of the four methods, and those results could not be used within this study to directly assess the methods. One laboratory did not have the capability to perform purge & trap analyses, and therefore did not submit data for VH/MAH in water. ASL and PESC jointly reviewed the submitted data to identify transcription errors and calculation errors 2. Results generated using significantly modified methods were excluded from statistical evaluation. Where potential errors were identified, PESC contacted the laboratories to confirm results. For confirmed errors, corrected results were used for the study. Results that failed critical Quality Control (QC) requirements of the methods were also excluded from statistical evaluation. All data exclusions are flagged and noted in Appendix A. Single Laboratory Results In conjunction with the BCMELP Petroleum Hydrocarbon Round Robin, ASL Analytical Service Laboratories carried out single laboratory validation of the methods using the same Reference Samples and QC Samples as were used in the round robin. To assess intra-laboratory variability, 1 About half of the 22 labs routinely analyze Petroleum Hydrocarbons for direct or indirect submission to BCMELP. 2 Laboratories are identified anonymously by number. Laboratory identities are known only to PESC. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 4 of 48

5 ASL performed each analysis with at least 6 replicates (typically 8-9). Single laboratory results also include Method Detection Limit (MDL) determination data. Summary of Round Robin and Single Laboratory Results Table 1 summarizes and compares the key results from the round robin and single laboratory studies. Note that since the true values for any of the hydrocarbon round robin samples are unknown, only method variability and comparability can be assessed. Table 1: COMPARSION OF ROUND ROBIN AND SINGLE LABORATORY RESULTS Round Robin Single Lab Round Robin Single Lab Units Mean %RSD Mean %RSD Mean %RSD Mean %RSD EPH in Water Low Level Method Spike High Level Method Spike EPH W10-19 ug/l % % % % EPH W19-32 ug/l % % % % Total PAH ug/l % % % % EPH in Solid RTC Reference Material (EPHRM1) NRC Reference Material HS3B (EPHRM2) EPH S10-19 mg/kg % % % % EPH S10-19 mg/kg % % % % Total PAHs mg/kg % % % % VPH in Water Low Level Method Spike High Level Method Spike VH W6-oXylene ug/l % % % % VH WoXylene-10 ug/l % % % % VH W6-10 ug/l % % % % Total BTEX ug/l % % % % VPH in Solids 3 Low Level Method Spike High Level Method Spike VH S6-oXylene mg/kg % % % % VH SoXylene-10 mg/kg % % % % VH S6-10 mg/kg % % % % Total BTEX mg/kg % % % % Table 1 shows that the means of the round robin study results agree very well with those of the single laboratory study. In most cases these means are within 10-20% of each other. This degree of consistency is very good considering the small sample size of much of the round robin data. As expected, single laboratory results were considerably more precise than round robin results. Single laboratory precision for the hydrocarbon parameters averaged 4-5% relative standard deviation (RSD). Inter-laboratory precision for the same parameters averaged 20-25% RSD. It is 3 VPH in Solids represents direct injection summary data only. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 5 of 48

6 particularly noteworthy that the inter-laboratory precision of the hydrocarbon parameters is typically better than that seen for the target MAH and PAH compounds. This was an encouraging (and unexpected) finding. Historically, petroleum hydrocarbon methods have exhibited unacceptable inter-laboratory variability and inconsistency. The need to reduce such variability was the primary reason behind the development of BC Environment s new hydrocarbon methods. It is also interesting to note that the inter-laboratory precision achieved in the current study was comparable to or better than the precision achieved in a similar round robin study of twenty-seven laboratories carried out by the Commonwealth of Massachusetts, Department of Environmental Protection in the Fall of DESIGN AND EXECUTION OF ROUND ROBIN STUDY Several factors complicated the selection of appropriate samples for this study. First, no reference materials are currently certified for the VH or EPH parameters. Furthermore, because the parameters are method-defined, the true values for VH and EPH can only be estimated, even for samples spiked with known amounts of petroleum products. Where feasible, commercially available reference materials were chosen for round robin solids samples, due to their homogeneity, proven stability, and ease of acquisition. For this study, two soil/sediment reference materials that contained EPH-range petroleum hydrocarbons were selected. The first, HS3B, is a marine harbour sediment material prepared by the National Research Council of Canada (Halifax). The second, CRM , is a soil which was fortified with diesel/motor oil specifically for this study by the Resource Technology Corporation of Wyoming (RTC). Suitable reference materials are not available for VH-range hydrocarbons in solids. Consequently, for this study, gasoline spikes into a wetted clean sand matrix were used as the VH solids Reference Samples. Aqueous spike samples of diesel and gasoline, respectively, were selected for the EPH and VH water Reference Samples. To avoid problems with sub-sampling and with degradation during transport and storage, participating laboratories were instructed to prepare their own aqueous Reference Samples using reagent water and the spike solutions provided. Participants were also provided with mixed solutions of specific alkane and aromatic hydrocarbons, for use in the methods Instrument Performance and Method Performance Checks. Instrument Performance Checks are used to measure and control the relative instrument responses of various VH and EPH components. Method Performance Checks are used to monitor and control losses of analyte throughout each procedure. Each participating laboratory was responsible for supplying and preparing its own instrument calibration standards. This procedure likely contributed to the variability of the inter-laboratory results. Participating laboratories were blind to the identities of 4 Commonwealth of Massachusetts, Executive Office of Environmental Affairs, Department of Environmental Protection, "Report on Results of the Fall 1997 VPH/EPH Round Robin Testing Program", January 12, Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 6 of 48

7 the reference materials, and to the types and concentrations of petroleum product spiking solutions used. The study was not designed to evaluate performance of MAH and PAH methodologies, but these parameters form an integral component of the VPH and LEPH/HEPH procedures. Consequently, participating laboratories were asked to report MAH and PAH results. Table 2 summarizes instructions provided to participants. Table 2: SUMMARY OF ROUND ROBIN INSTRUCTIONS Method Section Type 5 Sample Instructions EPHw 1.1 IP Solution 1 Dilute Solution 1 50 times in iso-octane. Analyze directly according to method. 1.2 MS Solution 1 Spike 20 ul of Solution 1 into 500 ml of reagent water. Analyze according to method. 1.3 MS Solution 2 Spike 50 ul of Solution 2 into 500 ml of reagent water. Analyze according to method. 1.4 MS Solution 2 Spike 250 ul of Solution 2 into 500 ml of reagent water. Analyze according to method. EPHs 2.1 IP Solution 1 Dilute Solution 1 50 times in iso-octane. Analyze directly according to method. 2.2 MS Solution 1 Spike 100 ul of Solution 1 directly into extraction vessel containing 10 grams of spike matrix and 2 ml reagent water. Analyze according to method. 2.3 RM EPHRM1 Weigh 10 grams of EPHRM1 into extraction vessel, add 2 ml reagent water. Analyze according to method. 2.4 RM EPHRM2 Weigh 10 grams of EPHRM2 into extraction vessel, add 2 ml reagent water. Analyze according to method. VHw 3.1 IP Solution 3 Dilute Solution 3 50 times in methanol. Spike 1 ul of solution for every 1 ml of purge water. Spike directly into purge vessel. Analyze according to method. 3.2 MS Solution 4 Spike 1ul of Solution 4 for every 1 ml of purge water. Spike directly into purge vessel. Analyze according to method. 3.3 MS Solution 4 Spike 5ul of Solution 4 for every 1 ml of purge water. Spike directly into purge vessel. Analyze according to method. VHs 4.1 IP Solution 3 Dilute Solution times in methanol. Analyze directly according to method. 4.2 MS Solution 3 Spike 220 ul of Solution 3 into 10 grams of spike matrix and 2 ml reagent water. Analyze according to method. 4.3 MS Solution 5 Spike 50 ul of Solution 5 into 10 grams of spike matrix and 2 ml reagent water. Analyze according to method. 4.4 MS Solution 5 Spike 250 ul of Solution 5 into 10 grams of spike matrix and 2 ml reagent water. Analyze according to method. 5 Sample Types: IP = instrument performance, MS = matrix spike, and RM = reference material. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 7 of 48

8 Table 3 lists the sources and descriptions of the round robin sample materials. TABLE 3: DESCRIPTION OF ROUND ROBIN STUDY MATERIALS Sample Manufacturer / Supplier Catalog # Description Solution 1 Crescent Chemical Company Inc., Hauppauge, NY CCS-115R2 5,000 ug/ml of each of nc10, nc12, nc16, nc19, nc20, nc30, nc32, nc40, Naphthalene, Phenanthrene, Pyrene, and Benzo(a)pyrene in 1:1 Dichloromethane:Carbon Disulfide some solutions were custom-made Solution 2 PDR-002A ,000 ug/ml diesel in acetone Solution 3 CCS-119R 5,000 ug/ml of each of nc6, nc8, nc10, Benzene, Ethylbenzene, Toluene, m-xylene, p-xylene, and o- Xylene in methanol. Solution 4 PGR-001M.20 2,000 ug/ml gasoline in methanol. Solution 5 PGR-001M ,000 ug/ml gasoline in methanol EPHRM1 Resource Technology Corporation, Laramie, WY CRM Reference Material, soil matrix fortified with diesel and motor oil. Not certified. EPHRM2 National Research Council Canada, Halifax, NS HS3B Reference Material, marine harbour sediment (certified for PAH). DISCUSSION OF ROUND ROBIN AND SINGLE LABORATORY RESULTS Summary results for the nine participating British Columbia and Alberta laboratories submitting results for this study are presented in Tables 4 through 18. Since the intent of the study was to evaluate inter-laboratory variability of the hydrocarbon methods as written, laboratories were asked to use the methods without modification wherever possible. Where laboratories used significantly modified methodologies, their results were excluded for calculation of mean and percent relative standard deviation data. Refer to Appendix A for the complete tabulation of round robin results, together with pertinent information on the methods used by each laboratory. Scientific justification for exclusion of data is also presented in Appendix A. Of the 9 laboratories that submitted data for EPH in Waters: All 9 labs followed the EPHw method with little or no modification. Of the 9 laboratories that submitted data for EPH in Solids: 7 labs followed the EPHs method with little or no modification. 1 lab used Dichloromethane as the extraction solvent. 1 lab used a different method of extraction and a different ratio of hexane and acetone. Of the 8 laboratories that submitted data for VH in waters: 7 labs followed the VHw method with little or no modification. 1 lab used headspace as the method of sample introduction. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 8 of 48

9 Of the 9 laboratories that submitted data for VH in solids: 6 labs followed the VHs method with little or no modification. 3 labs used purge & trap as the method of sample introduction. The single laboratory data produced by ASL is discussed below in comparison with the round robin results. For VH in Solids, the single lab data also includes an additional matrix spike, representing a higher concentration than either of the round robin VHs spikes. Single laboratory Method Detection Limit (MDL) results are reported in Table 19. A complete tabulation of the single laboratory results is provided in Appendix B. For comparison purposes, summary results for the single laboratory data are presented with corresponding round robin summary results in Tables 4 through 18. EPH in Water - Instrument Performance Check Table 4: EPHw INSTRUMENT PERFORMANCE CHECK (Part 1.1) Round Robin Results Single Lab Results Relative Response (n) Mean % RSD (n) Mean % RSD Decane (nc10) % % Naphthalene % % Dodecane (nc12) % % Hexadecane (nc16) % % Phenanthrene % % Nonadecane (nc19) % % Eicosane (nc20) n/a n/a Pyrene % % Benzo(a)pyrene % Triacontane (nc30) % % Dotriacontane (nc32) % % EPHw is analyzed by direct injection Gas Chromatography with Flame Ionization Detection (GC- FID). The EPHw Instrument Performance Check is a required QC component of the EPHw method. It is designed to ensure that the GC-FID instrument is operating such that the response of hydrocarbon components throughout the EPH range are approximately equal, thus preventing relative bias between higher and lower molecular weight EPH components, and making interlaboratory consistency possible. Instrument Performance Checks have been incorporated into the new BC Environment hydrocarbon methods. They are the primary measure of instrument performance for the methods, and they govern which modifications to instrumental components of the new methods are permissible under the performance based methods approach. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 9 of 48

10 Results for the EPHw Instrument Performance Check are reported as relative response, which is the GC-FID peak area of each specified component divided by the peak area of eicosane (nc20), where all components are present at the same concentration. A relative response of 1.00 indicates equal response between the specified component and nc20. The EPHw method states that the relative response versus nc20 of all compounds listed in Table 4 must fall between (except in the case of benzo(a)pyrene, for which monitoring is not required). Table 4 summarizes the results from the seven laboratories that passed (or almost passed) the method acceptance criteria for this sample. Data from two laboratories were excluded due to their extremely low relative responses in the nc30 to nc32 range. Results from those two laboratories were also excluded from statistical evaluations of other EPHw round robin samples. For both the round robin and single laboratory results, the mean relative response of all compounds in this sample (except benzo(a)pyrene) ranged from approximately This result indicates that the instrumental procedure specified in the EPHw method provides equivalent response throughout the EPH range of nc19 through nc32. EPH in Water - Method Performance Check Table 5: EPHw METHOD PERFORMANCE CHECK (Part 1.2) Round Robin Results Single Lab Results Spike Recovery (%) (n) Mean % RSD (n) Mean % RSD Decane (nc10) % 18.6% % 4.5% Naphthalene % 31.3% 8 101% 5.2% Dodecane (nc12) % 15.3% % 5.0% Hexadecane (nc16) % 18.1% 8 105% 5.5% Phenanthrene % 17.1% 8 105% 6.1% Nonadecane (nc19) % 17.9% 8 105% 5.6% Eicosane (nc20) % 17.0% 8 105% 5.6% Pyrene % 15.0% 8 106% 7.1% Benzo(a)pyrene % 19.9% 8 111% 6.0% Triacontane (nc30) % 19.3% 8 110% 6.1% Dotriacontane (nc32) % 20.4% 8 102% 5.5% The EPHw Method Performance Check is a required QC component of the EPHw method. It is designed to monitor potential losses of EPH components through the sample preparation steps of the method. It governs which modifications to sample preparation components of the new methods are permissible under the performance based methods approach. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 10 of 48

11 Results are reported as spike recovery, which is the measured concentration divided by the spiked concentration of each compound (in percent). The EPHw method states that the recovery of all compounds listed in Table 5 must normally range between 80% and 120% for nc13 through nc32, and between 65% and 120% for nc10, nc12, and naphthalene. For both the round robin and single laboratory results, the mean recoveries of most compounds ranged between %. This result indicates that the sample preparation procedures specified in the EPHw method can achieve reliable and consistent recoveries of compounds across the EPH range. Round robin mean recoveries were slightly low for nc10 (55%) and for nc12 (69%). These results indicate loss due to volatility. These losses are most likely due to minor difficulties with spiking techniques (see results for EPHs method performance spikes). However, they may also indicate losses of volatiles during extract concentration steps or during the extraction process. Recoveries for these compounds were much better within the single laboratory data. EPH in Water - Method Spikes Table 6: EPHw LOW LEVEL METHOD SPIKE (Part 1.3) Round Robin Results Single Lab Results EPH Results (ug/l) (n) Mean % RSD (n) Mean % RSD EPH W % % EPH W % % LEPHw % % HEPHw % % PAH Results (ug/l) (n) Mean % RSD (n) Mean % RSD Naphthalene % % Acenaphthene % 8 <0.5 n/a Fluorene % % Phenanthrene % % Anthracene 6 < n/a % Acridine 5 < n/a 8 <0.1 n/a Fluoranthene 6 < n/a 8 <0.05 n/a Pyrene % % Benz(a)anthracene 6 < n/a 8 <0.05 n/a Benzo(a)pyrene 7 < n/a 8 <0.05 n/a Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 11 of 48

12 Table 7: EPHw HIGH LEVEL METHOD SPIKE (Part 1.4) Round Robin Results Single Lab Results EPH Results (ug/l) (n) Mean % RSD (n) Mean % RSD EPH W % % EPH W % % LEPHw % % HEPHw % % PAH Results (ug/l) (n) Mean % RSD (n) Mean % RSD Naphthalene % % Acenaphthene % 8 <3 n/a Fluorene % % Phenanthrene % % Anthracene 4 < n/a % Acridine 6 < n/a 8 <0.5 n/a Fluoranthene 7 < n/a 8 <0.2 n/a Pyrene % % Benz(a)anthracene 7 < n/a 8 <0.05 n/a Benzo(a)pyrene 7 < n/a 8 <0.05 n/a Tables 6 and 7 summarize round robin and single laboratory results for two method spikes of diesel into reagent water. Comparative equivalency between single laboratory and round robin data is excellent. Round robin precision for EPH W10-19 and EPH W19-32 was two to three times better than that seen for the PAH parameters. The diesel concentrations of the spikes were 5,000 and 25,000 ug/l in water. There is no known true value for EPHw in diesel spikes. For the 5,000 ug/l diesel spike, total EPH (i.e. the sum of EPH W EPH W19-32 ) for round robin and single laboratory data averaged 3,726 and 3,949 ug/l respectively. These results indicate that approximately 20-25% of the components of this diesel product lie outside the nc10-nc32 range, assuming no losses during sample processing steps. The maximum reporting detection limit (DL) specified for each of EPH W10-19 and EPH W19-32 in the LEPH/HEPH Calculation Procedure is 250 ug/l. For EPH W10-19 in the low spike, mean results were approximately twelve times this level. For EPH W19-32, mean results were two times the maximum reporting DL. Method Detection Limits determined for single laboratory data were 59 ug/l for EPH W10-19 and 102 ug/l for EPH W Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 12 of 48

13 EPH in Solids - Instrument Performance Check Table 8: EPHs INSTRUMENT PERFORMANCE CHECK (Part 2.1) Round Robin Results Single Lab Results Relative Response (n) Mean % RSD (n) Mean % RSD Decane (nc10) % % Naphthalene % % Dodecane (nc12) % % Hexadecane (nc16) % % Phenanthrene % % Nonadecane (nc19) % % Eicosane (nc20) n/a n/a Pyrene % % Benzo(a)pyrene % % Triacontane (nc30) % % Dotriacontane (nc32) % % EPHs is analyzed by direct injection Gas Chromatography with Flame Ionization Detection (GC- FID). The EPHs Instrument Performance Check is a required QC component of the EPHs method. It is designed to ensure that the instrument is operating such that the response of hydrocarbon components throughout the EPH range are approximately equal, thus preventing relative bias between higher and lower molecular weight EPH components, and making good inter-laboratory consistency possible. The Instrument Performance Check is the primary measure of EPHs instrument performance. It governs which modifications to instrumental components of the new methods are permissible under the performance based methods approach. This sample is identical to that of the EPHw Instrument Performance Check in Table 4. Results for the EPHs Instrument Performance Check are reported as relative response, which is the GC-FID peak area of each specified component divided by the peak area of eicosane (nc20), where all components are present at the same concentration. A relative response of 1.00 indicates equal response between the specified component and nc20. The EPHs method states that the relative response versus nc20 of all compounds listed in Table 8 must fall between (except in the case of benzo(a)pyrene, for which monitoring is not required). Table 8 summarizes the results from the seven laboratories that passed (or almost passed) the method acceptance criteria for this sample. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 13 of 48

14 Data from two laboratories were excluded due to their extremely low relative responses in the nc30 through nc32 range. Results from those two laboratories were also excluded from statistical evaluations of other EPHs round robin samples. For both the round robin and single laboratory results, the mean relative response of all compounds (except benzo(a)pyrene) in this sample ranged from approximately This result indicates that the instrumental procedure specified in the EPHs method provides equivalent response throughout the EPH range of nc19 through nc32. EPH in Solids - Method Performance Check Table 9: EPHs METHOD PERFORMANCE CHECK (Part 2.2) Round Robin Results Single Lab Results Spike Recovery (%) (n) Mean % RSD (n) Mean % RSD Decane (nc10) % 89.0% % 4.6% Naphthalene % 52.2% % 3.5% Dodecane (nc12) % 60.7% % 3.6% Hexadecane (nc16) % 15.2% % 2.8% Phenanthrene % 25.8% % 3.5% Nonadecane (nc19) % 20.1% % 1.7% Eicosane (nc20) % 23.7% % 1.5% Pyrene % 41.8% % 1.7% Benzo(a)pyrene % 45.0% % 6.5% Triacontane (nc30) % 8.4% % 1.7% Dotriacontane (nc32) % 17.9% % 1.7% The EPHs Method Performance Check is a required QC component of the EPHs method. It is designed to monitor potential losses of EPH constituents through the sample preparation steps of the method. It governs which modifications to sample preparation components of the new methods are permissible under the performance based methods approach. Results are reported as spike recovery, which is the measured concentration divided by the spiked concentration of each compound (in percent). The EPHs method states that the recovery of all compounds listed in Table 9 must normally range between 80% and 120% for nc13 through nc32, and between 65% and 120% for nc10, nc12, and naphthalene. Round robin results for this sample were highly variable, due to a problem with the spiking technique that was not identified until after the study had begun. The round robin instructions specified the addition of 100uL of a spiking solution into 10 g of sand matrix plus 2 ml reagent water (Initial instructions specified 20uL of the spiking solution. However, this was changed to 100 ul in a letter of correction subsequently sent to participating laboratories). The sample was then to be dried with diatomaceous earth prior to Soxhlet extraction. Since the spiking solution was Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 14 of 48

15 prepared in a highly volatile solvent mixture, and because such a small volume of the solution was added, evaporative losses during the drying step were severe. Prior to the generation of the single laboratory data, the spiking problem was corrected by preparing the spike solution in iso-octane, a much less volatile solvent, and by adding a larger volume of the spike solution (1 ml) to Method Performance Check samples. Iso-octane simulates the presence of organic matter which is otherwise absent in a clean sand matrix (but which is normally present in soils and most sediments). If the spike matrix contains no organic matter, spiked volatile organics are lost much more quickly to evaporation. The corrected spiking procedure will be included the finalized version of the EPHs method. Single laboratory data generated using the modified spiking technique achieved mean recoveries ranging between % for all analytes except benzo(a)pyrene, which had a mean recovery of 74%. This result indicates that the sample preparation procedures specified in the corrected EPHs method can yield reliable and consistent recoveries of compounds across the EPH range. EPH in Solids - Analysis of Reference Materials Table 10: EPHs REFERENCE MATERIAL 1 - RTC TPH (Part 2.3) Round Robin Results Single Lab Results EPH Results (mg/kg) (n) Mean % RSD (n) Mean % RSD EPH S % % EPH S % % LEPHs % % HEPHs % % PAH Results (mg/kg) (n) Mean % RSD (n) Mean % RSD Naphthalene % % Phenanthrene % % Pyrene % % Benz(a)anthracene % % Benzo(b)fluoranthene % % Benzo(k)fluoranthene % % Benzo(a)pyrene % % Indeno(1,2,3-cd)pyrene % % Dibenz(a,h)anthracene % % Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 15 of 48

16 Table 11: EPHs REFERENCE MATERIAL 2 - NRC Canada HS3B (Part 2.4) Round Robin Results Single Lab Results EPH Results (mg/kg) (n) Mean % RSD (n) Mean % RSD EPH S % % EPH S % % LEPHs % % HEPHs % % PAH Results (mg/kg) (n) Mean % RSD (n) Mean % RSD Naphthalene % % Phenanthrene % % Pyrene % % Benz(a)anthracene % % Benzo(b)fluoranthene % % Benzo(k)floranthene % % Benzo(a)pyrene % % Indeno(1,2,3-cd)pyrene % % Dibenz(a,h)anthracene % % Tables 10 and 11 present summarized round robin and single laboratory results for two commercially available sediment/soil reference materials (RMs). Each RM was wetted prior to extraction. Comparative equivalency between the single laboratory and round robin data is excellent. Round robin precision for EPH S10-19 and EPH S19-32 is consistently better than that seen for PAH parameters. Reference Material 1 (RTC CRM-355) is a soil fortified with a diesel / motor oil mixture. Resource Technology Corporation (Laramie, Wyoming) produced this RM specifically for this study. This RM has not been dried, consequently it contains a significant portion of lighter EPH constituents. Reference Material 2 (NRC HS3B) is a marine harbour sediment which has been dried and sieved. It is produced by the National Research Council of Canada (Halifax), and is certified for PAH content. EPH content of this RM is primarily in the nc19-nc32 range. Results from two laboratories were excluded due to the use of significantly modified methods. One lab used a DCM Soxhlet extraction, and the other used DCM shaker extraction. The method requires the use of 1:1 hexane:acetone as the extraction solvent. As with the EPHw diesel spikes, there is no true value for EPHs in either of these materials. Round robin and single laboratory precision was better for reference material 1 (i.e. the RTC RM) than for reference material 2 (i.e. the NRC RM). This is likely due to the higher concentrations Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 16 of 48

17 inherent in reference material 1. However, it is also possible that reference material 1 may be easier to extract, since it is a fortified material. The maximum reporting detection limit (DL) specified for EPH S10-19 and EPH S19-32 in the LEPH/HEPH Calculation Procedure is 500 mg/kg. Reference material 2 (i.e. the NRC RM) contains EPH S10-19 at a concentration approximately equal to 500 mg/kg, and contains EPH S19-32 at about five times this level. Reference material 1 (i.e. the RTC RM) contains both EPH parameters at approximately 7-10 times the maximum reporting DL. Method Detection Limits determined for the single laboratory data were 21 mg/kg for EPH S10-19 and 9 mg/kg for EPH S VH in Water - Instrument and Method Performance Check Table 12: VHw INSTRUMENT / METHOD PERFORMANCE CHECK (Part 3.1) Round Robin Results Single Lab Results Relative Response (n) Mean % RSD (n) Mean % RSD Hexane (nc6) % % Benzene % % Toluene % % Octane (nc8) % % Ethylbenzene % % m,p-xylene n/a n/a o-xylene % % 1,2,4-Trimethylbenzene n/a n/a Decane (nc10) % % VHw is analyzed by Purge and Trap - Gas Chromatography with Flame Ionization Detection (P&T- GC-FID). The VHw Instrument / Method Performance Check is a required QC component of the VHw method. It is designed to ensure that the P&T-GC-FID instrument is operating such that the response of hydrocarbon components throughout the VH range are approximately equal, thus preventing relative bias between higher and lower molecular weight VH components, or between aliphatic and aromatic VH components. This step enhances inter-laboratory consistency. The Instrument / Method Performance Check is the primary measure of VHw method performance. It governs which modifications to instrumental and sample preparation components of the new methods are permissible under the performance based methods approach. 6 7 Relative response calculated against m,p-xylene. Relative response calculated against 1,2,4-Trimethybenzene. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 17 of 48

18 For VHw, the instrument and method performance checks are combined, because water samples analyzed by purge and trap require no additional sample extraction or sample processing steps. Thus, for VHw, an Instrument Performance Check is identical to a Method Performance Check. Results for the VHw Instrument/Method Performance Check are reported as relative response, which is the GC-FID peak area of each specified component divided by the peak area of m,p-xylene or 1,2,4-trimethylbenzene, where all components are present at the same concentration. A relative response of 1.00 indicates equal response between the two compounds. The VHw method states that the relative response (versus m,p-xylene or 1,2,4-trimethylbenzene) of all compounds listed in Table 12 must fall between Table 12 summarizes the results from the five laboratories that followed the required analysis procedure, and that passed the method acceptance criteria for this sample. Data from three laboratories were excluded due to poor relative responses of one or more components, or due to the failure to use purge and trap instrumentation. Results from these laboratories were also excluded from statistical evaluations of other VHw round robin samples. One of the three labs used the headspace technique, which is not permitted in the VHw method, since it is known to exacerbate relative bias between aliphatic and aromatic compounds. (Note the bias of up to +275% for aliphatics in the results presented for lab 8 in Appendix A, Part 3.1, VPHw Instrument and Method Performance Check). For both the round robin and single laboratory results, the mean relative response of most compounds in this sample ranged from approximately Mean relative response for decane was slightly lower at These results indicate that the instrumental procedure specified in the VHw method can achieve equivalent response throughout most of the VH range, with a slight decline in the nc9-nc10 region. Note that a decline in purge and trap instrument response in the nc9-nc10 region was the reason that the VH Draft 2.0 methods were modified to use a two-range calibration mode. The nc6 to ortho-xylene range is now calculated against meta-xylene, and the ortho-xylene to nc10 range is now calculated against 1,2,4-trimethylbenzene. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 18 of 48

19 VH in Water Method Spikes Table 13: VHw LOW LEVEL METHOD SPIKE (Section 3.2) EPH W6-oXylene Round Robin Results Single Lab Results EPH S19-32 VH Results(ug/L) (n) Mean % RSD (n) Mean % RSD VH W6-oXylene % % VH WoXylene % % VH W % % VPHw % % BTEX Result (ug/l) (n) Mean % RSD (n) Mean % RSD Benzene % % Toluene % % Octane (nc8) % % Ethylbenzene % % m,p-xylene % % o-xylene % % Table 14: VHw HIGH LEVEL METHOD SPIKE (Section 3.3) Round Robin Results Single Lab Results VH Results(ug/L) (n) Mean % RSD (n) Mean % RSD VH W6-oXylene % % VH WoXylene % % VH W % % VPHw % % BTEX Result (ug/l) (n) Mean % RSD (n) Mean % RSD Benzene % % Toluene % % Ethylbenzene % % m,p-xylene % % o-xylene % % Tables 13 and 14 present summarized round robin and single laboratory results for two method spikes of gasoline into reagent water. Comparative equivalency between single laboratory and round robin data is very good. Round robin precision for VH W6-10 was approximately equal to that for the MAH (i.e. BTEX) parameters. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 19 of 48

20 Gasoline concentrations of the spikes were 2,000 and 10,000 ug/l in water. There is no known true value for VHw in the gasoline spikes. For the 2,000 ug/l spike, VH W6-10 in round robin and single laboratory data average 1010 and 1033 ug/l respectively. This result indicates that approximately 50% of the composition of this gasoline product lies outside the nc6-nc10 range, assuming no losses during sample preparation steps. The maximum reporting detection limit (DL) specified for VH W6-10 in the VPH Calculation Procedure is 100 ug/l. For VH W6-10 in the low spike, mean results were approximately ten times this level. The Method Detection Limit for VH W6-10, determined for the single laboratory data, was 13 ug/l. For the analysis of BTEX, five labs used GC with Mass Spectrometric detection (GC/MS), which is the preferred instrument. One lab used GC with Photo Ionization Detection (GC/PID). The GC/MS and the GC/PID results exhibited reasonable consistency for these samples. Two labs used GC with Flame Ionization Detection (GC/FID). GC/FID results were less consistent than GC/MS or GC/PID results for these samples. VH in Solids Instrument Performance Check Table 15: VPHs INSTRUMENT PERFORMANCE CHECK (Part 4.1) Round Robin Results Single Lab Results Direct Injection Purge & Trap Direct Injection Relative Response (n) Mean % RSD (n) Mean % RSD (n) Mean % RSD Hexane (nc6) % % % Benzene % % % Toluene % % % Octane (nc8) % % % Ethylbenzene % % % m,p-xylene n/a n/a n/a o-xylene % % % 1,2,4-Trimethylbenzene n/a n/a n/a Decane (nc10) % % % VHs is analyzed by direct injection Gas Chromatography with Flame Ionization Detection (GC- FID). The VHs Instrument Performance Check is a required QC component of the VHs method. It is designed to ensure that the GC-FID instrument is operating such that the response of hydrocarbon components throughout the VH range are approximately equal, thus preventing relative bias 8 9 Relative response calculated against m,p-xylene. Relative response calculated against 1,2,4-Trimethybenzene. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 20 of 48

21 between higher and lower molecular weight VH components, or between aliphatic and aromatic VH components. This step enhances inter-laboratory consistency. The Instrument Performance Check is the primary measure of VHs instrument performance. It governs which modifications to instrumental components of the new methods are permissible under the performance based methods approach. Results are reported as relative response, which is the GC-FID peak area of each specified component divided by the peak area of meta,para-xylene or 1,2,4-trimethylbenzene, where all components are present at the same concentration. A relative response of 1.00 indicates equal response between the two compounds. The VHs method states that the relative response (versus m,p-xylene or 1,2,4-trimethylbenzene) of all compounds listed in Table 15 must fall between Table 15 summarizes the results from the seven laboratories that passed the method acceptance criteria for this sample. Results for two different analytical techniques (i.e. direct injection and purge & trap) are summarized independently. Data from two laboratories were excluded due to poor relative responses of one or more components. Three laboratories used purge & trap instrumentation for the VHs round robin samples. Purge & trap is not the reference technique called for by this method. However, it is permitted as an alternative procedure under the performance based method approach (laboratories must first demonstrate equivalence to the reference procedure). Therefore, direct injection results and purge and trap results were summarized separately. The direct injection results demonstrate the performance of the VHs method as written. The purge & trap summary results are provided for reference purposes only. However, comparison of the results for the two techniques does indicate that equivalence between them can probably be achieved. (Note the small sample population for the purge & trap method, with n=2). For both single laboratory and round robin results by either direct injection or purge & trap, the mean relative response of most compounds in this sample ranged from approximately , with two exceptions: The direct injection procedure exhibited a slight low-bias for hexane, with a relative response was approximately 0.8 relative to m,p-xylene. The purge and trap procedure exhibited a slight low-bias for decane, with a relative response of approximately 0.8 relative to 1,2,4-trimethylbenzene. Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 21 of 48

22 Both instrumental procedures are capable of generating equivalent response throughout most of the VH range, but direct injection exhibits slightly lower relative response in the nc6-nc7 region, and purge & trap shows exhibits slightly lower relative response in the nc9-nc10 region. Note that the decreased response of purge and trap in the nc9-nc10 region was the reason that the VH Draft 2.0 methods were modified to use a two-range calibration mode. Without this change, the use of purge and trap bias would cause a much more significant negative bias in VH results. The nc6 to o-xylene range is now calculated against m-xylene, and the o-xylene to nc10 range is now calculated against 1,2,4-trimethylbenzene. VH in Solids Method Performance Check Table 16: VPHs METHOD PERFORMANCE CHECK (Part 4.2) Round Robin Results Single Lab Results Direct Injection Purge & Trap Direct Injection Spike Recovery (%) (n) Mean % RSD (n) Mean % RSD (n) Mean % RSD Hexane (nc6) 4 102% 4.7% % 8.6% % 10.4% Benzene 5 104% 4.1% 2 104% 5.3% 8 101% 7.0% Toluene 5 105% 5.9% 2 102% 0.1% 8 100% 5.8% Octane (nc8) 5 103% 4.8% 2 103% 3.1% % 8.1% Ethylbenzene 5 106% 3.9% 2 100% 3.5% 8 100% 5.3% m,p-xylene 5 106% 4.0% 2 103% 0.2% 8 100% 5.4% o-xylene 5 106% 4.2% 2 102% 0.9% 8 101% 5.9% 1,2,4-Trimethylbenzene 5 109% 3.5% 2 105% 3.6% 8 103% 6.7% Decane (nc10) 5 105% 4.9% 2 110% 4.8% % 7.2% The VHs Method Performance Check is a required QC component of the VHs method. It is designed to monitor potential losses of VH range components through the sample preparation steps of the method. It governs which modifications to sample preparation components of the new methods are permissible under the performance based methods approach. Results are reported as spike recovery, which is the measured concentration divided by the spiked concentration of each compound (in percent). The VHs method states that the recovery of all compounds listed in Table 16 must normally range between 80% and 120%. The round robin and single laboratory results were highly comparable, exhibiting mean recoveries ranging from %. This indicates that the sample preparation procedures specified in the VHs method can generate reliable and consistent recoveries for compounds across the VH range. Round robin precision for this sample was excellent. (Note that in this case, round robin precision is actually better than for the single laboratory). Prepared by S.A. Hannam and M. Hugdahl, ASL Analytical Service Laboratories ltd. 22 of 48